WO1999059921A1 - Procede de production de fines particules spheriques de carbonate ou d'hydroxyde de nickel, cobalt ou cuivre - Google Patents

Procede de production de fines particules spheriques de carbonate ou d'hydroxyde de nickel, cobalt ou cuivre Download PDF

Info

Publication number
WO1999059921A1
WO1999059921A1 PCT/JP1999/002634 JP9902634W WO9959921A1 WO 1999059921 A1 WO1999059921 A1 WO 1999059921A1 JP 9902634 W JP9902634 W JP 9902634W WO 9959921 A1 WO9959921 A1 WO 9959921A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbonate
nickel
ammonia
cobalt
hydroxide
Prior art date
Application number
PCT/JP1999/002634
Other languages
English (en)
Japanese (ja)
Inventor
Kazuhiko Nagano
Kazunobu Abe
Shigefumi Kamisaka
Kiyoshi Fukai
Tsutoma Hatanaka
Shinji Ohgama
Hiroshi Nakao
Minoru Yoneda
Hideto Mizutani
Original Assignee
Sakai Chemical Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sakai Chemical Industries, Ltd. filed Critical Sakai Chemical Industries, Ltd.
Priority to KR1020007000618A priority Critical patent/KR100618071B1/ko
Priority to US09/463,021 priority patent/US6197273B1/en
Priority to EP99921191A priority patent/EP1013610B1/fr
Priority to DE69911559T priority patent/DE69911559T2/de
Publication of WO1999059921A1 publication Critical patent/WO1999059921A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/06—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/026—Spray drying of solutions or suspensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C01B13/328—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process by processes making use of emulsions, e.g. the kerosine process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/06—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/90—Stabilisation; Use of additives

Definitions

  • the present invention relates to a method for producing fine spherical particles of hydrate.
  • the present invention relates to a method for producing fine spherical particles of carbonate or hydroxide of an element selected from nickel, steel and cobalt, and more particularly, to a uniform fine spherical particle of a metal selected from nickel, copper and cobalt.
  • Nickel, cobalt, or copper carbonate which is particularly useful as a precursor for the production of fine powders of aluminum, and also useful as an organic synthesis catalyst, carrier, pigment, filler, glaze, etc.
  • the present invention relates to a method for producing fine spherical particles of hydroxide. Description of conventional technology
  • nickel carbonate particles are usually known only as amorphous or non-spherical fine powders, and are slightly described in Japanese Patent Application Laid-Open No. 2-59432, a WZO type emulsion.
  • a method for producing fine and spherical nickel carbonate particles by a method of using as a reaction field is described. That is, according to this method, for example, an aqueous solution of a water-soluble nickel salt such as nickel chloride is added to a non-aqueous medium together with a surfactant, and the mixture is stirred to prepare a WZO type emulsion.
  • An aqueous solution of a metal carbonate or bicarbonate is added as a neutralizing agent, and the aqueous solution of a nickel salt forming minute droplets in the emulsion is reacted with the neutralizing agent to form fine particles. This is to produce spherical nickel carbonate particles.
  • the emulsion is easily dissolved by the effect of the neutralizing agent used and salts produced as a by-product together with the water-insoluble nickel salt. Throughout the whole, it is difficult to secure a stable reaction field, and thus a spherical nickel with a fine particle size is obtained. It is difficult to obtain Kel salt particles.
  • the present invention has been made in order to solve the above-mentioned problems in the production of spherical particles having a fine particle diameter of carbonate or hydroxide of cobalt or copper, in addition to nickel. It is an object of the present invention to provide a method for producing fine spherical particles of an elemental carbonate, basic carbonate or hydroxide. Summary of the Invention
  • a carbonate or hydroxide of nickel, cobalt or copper represented by the following formula is dissolved in an aqueous ammonia solution, and the obtained aqueous solution is converted into a W / 0 emulsion in which the droplets of the aqueous solution are suspended in a non-aqueous medium. It is characterized in that a basic carbonate or hydroxide of nickel, cobalt or copper is precipitated in the droplets except for a vaporizable component containing ammonia from the droplets.
  • FIG. 1 is an X-ray diffraction diagram of the basic nickel carbonate particles obtained in Example 1.
  • FIG. 2 is a scanning electron micrograph of the basic nickel carbonate particles obtained in Example 1.
  • FIG. 3 is a particle size distribution diagram of the basic nickel carbonate particles obtained in Example 1.
  • FIG. 4 is an X-ray diffraction diagram of fine metal nickel powder obtained by oxidizing the basic nickel carbonate particles obtained in Example 1 and then reducing by heating in a hydrogen stream.
  • FIG. 5 is a scanning electron micrograph of the metallic nickel fine powder of FIG.
  • FIG. 6 is a particle size distribution diagram of the metal nickel fine powder of FIG.
  • FIG. 7 is an X-ray diffraction diagram of the basic nickel carbonate particles obtained in Example 4.
  • FIG. 8 is a scanning electron micrograph of the basic nickel carbonate particles obtained in Example 4.
  • FIG. 9 is an X-ray diffraction diagram of the basic nickel carbonate particles obtained in Example 11.
  • FIG. 10 is a scanning electron micrograph of the basic nickel carbonate particles obtained in Example 11.
  • FIG. 11 is an X-ray diffraction diagram of the basic nickel carbonate particles obtained in Example 14.
  • FIG. 12 is a scanning electron micrograph of the basic nickel carbonate particles obtained in Example 14.
  • FIG. 13 is an X-ray diffraction diagram of the basic nickel carbonate particles obtained in Example 19.
  • FIG. 14 is a scanning electron micrograph of the basic nickel carbonate particles obtained in Example 19.
  • FIG. 15 is an X-ray diffraction diagram of the nickel hydroxide particles obtained in Example 20.
  • FIG. 16 is a scanning electron micrograph of the nickel hydroxide particles obtained in Example 20.
  • FIG. 17 is an X-ray drawing of the basic nickel carbonate particles obtained in Example 22.
  • FIG. 18 is a scanning electron micrograph of the basic nickel carbonate particles obtained in Example 22.
  • FIG. 19 is an X-ray diffraction diagram of the basic nickel carbonate particles obtained in Example 33.
  • FIG. 20 is a scanning electron micrograph of the basic nickel carbonate particles obtained in Example 33.
  • FIG. 21 is an X-ray diffraction diagram of the nickel hydroxide particles obtained in Example 34.
  • FIG. 22 is a scanning electron micrograph of the nickel hydroxide particles obtained in Example 34.
  • FIG. 23 is an X-ray diffraction diagram of the basic copper carbonate particles obtained in Example 35.
  • FIG. 24 is a scanning electron micrograph of the basic copper carbonate particles obtained in Example 35.
  • FIG. 25 is an X-ray diffraction diagram of the basic cobalt carbonate particles obtained in Example 36.
  • FIG. 26 is a scanning electron micrograph of the basic cobalt carbonate particles obtained in Example 36.
  • FIG. 27 is a scanning electron micrograph of the basic nickel carbonate particles obtained in Example 37. DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION
  • Nickel, cobalt or copper carbonate or hydroxide represented by the following formula is dissolved in an aqueous ammonia solution, and the obtained aqueous solution is converted into a WZO type emulsion in which the droplets of the aqueous solution are suspended in a non-aqueous medium.
  • Nickel, cobalt or copper carbonate or hydroxide can be obtained as fine spherical particles.
  • M represents Ni, C0 or Cu, and accordingly, as a starting material, a carbonate or hydroxide of nickel, cobalt or copper is used.
  • X and y are numbers satisfying 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 2.
  • x + y 2.
  • ⁇ indicates nickel, cobalt, or copper as described above.
  • the starting material is not limited to a carbonate or hydroxide of a single element, but may be a carbonate or hydroxide of two or more of nickel, cobalt and copper. There may be. If necessary, the starting material may contain an element other than nickel, cobalt and copper. In addition, the above-mentioned starting material may contain a trivalent nickel ion or an ion such as calcium, cerium, yttrium, or iron as long as the formation of the below-described emulsion is not inhibited.
  • a carbonate / hydroxide of nickel, cobalt or copper is dissolved in an aqueous ammonia solution, and the obtained aqueous solution is subjected to droplets of the aqueous solution in a non-aqueous medium.
  • the nickel, cobalt or copper carbonate or hydroxide is extracted from the emulsion droplets by evaporating a vaporizable component containing ammonia from the emulsion droplets. Let Neutralize the droplets by adding force to the emulsion or acid to the emulsion.
  • the same carbonate as the starting material is obtained as a product.
  • an aqueous ammonia solution is used as an aqueous solution for dissolving the carbonate, or an aqueous solution containing other basic compounds other than ammonia together with ammonia is used. Also, the same carbonate as the starting material is obtained as the product.
  • the product obtained depends on the reaction conditions. That is, the aqueous solution for dissolving the hydroxide is ammonium carbonate, ammonium hydrogencarbonate, alkali metal carbonate or hydrogencarbonate together with the ammonia (these are sometimes referred to as carbonate (hydrogen) salts for the sake of simplicity).
  • carbonate can be obtained as a product, but the aqueous solution that dissolves the hydroxide contains ammonia as a basic compound, but the above-mentioned ammonia (carbon) does not contain carbonate.
  • the same hydroxide as the starting material can be obtained as a product.
  • a carbonate is used as a starting material, and is obtained by dissolving it in an aqueous ammonia solution or an aqueous solution containing ammonia and another basic compound other than ammonia. After converting the aqueous solution into a W / 0 type marsion containing droplets of the above aqueous solution in a non-aqueous medium, nickel, cobalt, or nickel or cobalt is removed in the droplets except for the vaporizable components that contain ammonia from the droplets. By precipitating the copper carbonate, fine spherical particles of nickel, cobalt or copper carbonate can be obtained, this embodiment being the most preferred according to the present invention.
  • nickel carbonate is dissolved in ammonia bicarbonate or an aqueous solution of ammonium carbonate together with ammonia in a pH range of 8.0 to 11.5, and the resulting aqueous solution of nickel salt is dissolved in non-aqueous solution.
  • the resulting emulsion is mixed with an aqueous medium to form emulsion, and then the emulsion is suctioned under reduced pressure to evaporate a vaporizable component (eg, carbon dioxide or water) containing ammonia from the aqueous solution of the nickel salt.
  • a vaporizable component eg, carbon dioxide or water
  • Nickel carbonate is precipitated in the droplets of the emulsion and collected, thereby obtaining fine spherical nickel carbonate particles.
  • the starting material nickel or cobalt or copper carbonate or hydroxide may be produced by any means or method.
  • carbonates can be obtained by neutralizing inorganic or organic acid salts such as chlorides, sulfates, nitrates, and acetates with alkali carbonates containing carbonate ions such as sodium carbonate and ammonium carbonate. it can.
  • an inorganic acid such as chloride, sulfate, nitrate or acetate of the above element is used.
  • a salt or an organic acid salt may be dissolved in an aqueous ammonia solution and, if necessary, reacted.
  • the aqueous ammonia solution when dissolving the starting material nickel, cobalt or copper carbonate or hydroxide in the aqueous ammonia solution, preferably contains other basic compounds other than ammonia.
  • the second basic compound is selected from the above-mentioned carbonate (hydrogen) salts (that is, ammonium carbonate, ammonium hydrogen carbonate, alkali metal carbonate, alkali metal bicarbonate), alkali metal hydroxides and amines. There is at least one species.
  • alkali metal for example, lithium, potassium or sodium is preferable.
  • alkali metal carbonate, alkali metal bicarbonate or alkali metal hydroxide include lithium carbonate, lithium bicarbonate, carbon dioxide lime, hydrogen bicarbonate, sodium carbonate, sodium bicarbonate, and the like.
  • examples thereof include lithium hydroxide, potassium hydroxide, and sodium hydroxide.
  • the amines are not particularly limited, but, for example, mono-, di- or trialkylamines, mono-, di- or trialkanolamines are preferably used. In the present invention, among such second basic compounds, ammonium bicarbonate is particularly preferably used.
  • nickel carbonate is dissolved in an aqueous ammonia solution containing the second basic compound, and the obtained aqueous solution of the nickel salt is dissolved in a non-aqueous medium.
  • the vaporizable components mainly ammonia and carbon dioxide gas
  • the carbon dioxide is contained in the droplets of the emulsion.
  • the nigel is precipitated, and if necessary, the vaporizable components mainly consisting of water are further evaporated from the emulsion droplets, and the nickel carbonate in the droplets is dried in oil, and the carbon dioxide thus obtained is dried. If the nickel is centrifuged, washed, and dried, for example, the desired fine spherical particles of nickel carbonate can be obtained.
  • nickel hydroxide is dissolved in an aqueous ammonia solution containing a carbonate (hydrogen) salt as the second basic compound, and the resulting aqueous solution of the nickel salt is dissolved in a non-aqueous medium.
  • a vaporizable component including ammonia mainly, ammonia and carbon dioxide is evaporated from the droplet to form a droplet in the emulsion.
  • Nickel carbonate is precipitated from the emulsion and, if necessary, the vaporizable component mainly consisting of water is further evaporated from the emulsion droplets, and the nickel carbonate in the droplets is dried in oil, and the pressure is reduced. If the obtained nickel carbonate is centrifuged, washed, and dried, for example, the desired fine spherical particles of nickel carbonate can be obtained.
  • nickel hydroxide is dissolved in an aqueous ammonia solution, and the obtained aqueous solution is converted into a W / 0 emulsion containing droplets of the aqueous solution in a non-aqueous medium.
  • the nickel hydroxide precipitates in the emulsion droplets by evaporating the ammonia from the water, and, if necessary, further evaporates the water from the emulsion droplets to obtain nickel hydroxide in the droplets.
  • the resulting nickel hydroxide is dried in oil, and the thus obtained nickel hydroxide is centrifuged, washed, and dried, for example, to obtain the desired spherical particles of nickel hydroxide.
  • the pH of the aqueous solution when nickel carbonate is dissolved in the aqueous ammonia solution is not particularly limited, but the pH is preferably in the range of 8.0 to 11.5.
  • the pH of the aqueous solution in which nickel carbonate is dissolved can be easily adjusted by using the above-mentioned various second basic compounds together with ammonia, preferably, the above-mentioned (hydrogen) carbonate. Nickel carbonate can be easily dissolved.
  • the concentration of the aqueous nickel salt solution obtained by dissolving nickel carbonate in an aqueous ammonia solution is not particularly limited, but is usually from 0.1 mol / L to a saturated concentration as Nigel metal. And particularly preferably in the range of 0.3 to 1.2 mol ZL.
  • the nickel salt aqueous solution thus obtained is mixed and stirred with a non-aqueous medium in the presence of a surfactant to prepare a emulsion according to a conventional method.
  • a non-ionic surfactant having a higher hydrophilicity is added to the nickel salt aqueous solution, and if necessary, the mixture is heated to a temperature of 5O'C or lower so as to prevent ammonia from evaporating and dissolved.
  • a more lipophilic strong nonionic surfactant is added to the non-aqueous medium, and if necessary, heated to dissolve.
  • the above-mentioned nickel salt aqueous solution is gradually added to the non-aqueous medium, and the nickel salt aqueous solution is finely dispersed to form a W / 0 type emulsion.
  • the average particle size and particle size distribution of the spherical nickel carbonate particles finally obtained are based on the size (average particle size) of the aqueous phase (droplets) in the emulsion, the particle size distribution, and the concentration of the aqueous solution of the salt solution.
  • the size (average particle size) and particle size distribution of the droplets in the emulsion are determined by the combination and amount of each surfactant used, the type of disperser, and the stirring speed by the disperser. Etc. can be adjusted.
  • the obtained carbonated nickel The average particle size of the gel particles can be arbitrarily adjusted in the range of 0.1 to 100 m, preferably in the range of 0.1 to 50 m.
  • a uniform fine particle made of nickel, cobalt or copper carbonate or hydroxide can be obtained.
  • Spherical particles can be obtained.
  • the non-aqueous medium for preparing the emulsion is preferably a water-insoluble, water-insoluble, and stable solvent which does not easily evaporate during the treatment under reduced pressure or normal pressure, as described below. Those having a higher boiling point are preferably used.
  • non-aqueous media examples include aliphatic hydrocarbons such as n-octene, isooctene, squalane, kerosene, etc., alicyclic hydrocarbons such as cyclooctane, cyclononane and cyclodecane, toluene, ethylbenzene, and the like.
  • Aromatic hydrocarbons such as isopropylbenzene, cumene, mesitylene and tetralin; ethers such as butyl ether and isobutyl ether; halogenated hydrocarbons such as dichloropentane; n-propyl acetate And fatty acid esters such as n-butyl acetate, isoptyl acetate, n-amyl acetate, isoamyl acetate, isoptyl propionate, ethyl acetate, and butyl butyrate, and mixtures thereof.
  • synthetic oils such as mineral oil, animal and vegetable oils and other natural oils, hydrocarbon oils, ester oils, ether oils, fluorinated lubricating oils, lubricating lubricating oils, lubricating lubricating oils, etc. It can be exemplified as a specific example of the medium.
  • a hydrocarbon organic solvent which is insoluble in water and has a low vapor pressure is preferable.
  • an aliphatic hydrocarbon solvent having a boiling point of 100 or more at normal pressure is preferably used.
  • the non-aqueous medium does not need to have a low vapor pressure, and a low-boiling non-aqueous medium can be used.
  • the surfactant used for preparing the emulsion is appropriately selected according to the non-aqueous medium used.
  • a highly hydrophilic surfactant having an HLB value of 10 or more is dissolved in the aqueous solution (aqueous phase) of the nickel salt in advance.
  • the amount of the surfactant to be used may be appropriately selected depending on the WZO ratio in the emulsion, the required particle size, and the like, and is not particularly limited, but is usually 20% by weight or less based on the emulsion. Preferably, it is in the range of 0.5 to 15% by weight. As described below, when the surfactant is dissolved in both the aqueous phase and the oil phase, the amount of the surfactant used is usually 20% by weight with respect to the aqueous or non-aqueous medium, respectively. %, Preferably in the range of 0.5 to 10% by weight.
  • the W / 0 ratio in the emulsion is determined by the amount and properties of the non-aqueous medium used, in particular, the viscosity and the surfactant used. In order to obtain a stable emulsion depending on the properties, especially the HLB value, it is usually in the range of 3Z2 to 1Z10, preferably 1 to 1/5, particularly preferably 13 to 1 / 5 range. However, it is not limited to this.
  • Nonionic surfactants having an HLB value of 10 or more such as polyoxyethylene sorbitan monolaurate, polyoxyxylene sorbitan monopalmitate, polyisoxylene sorbitan monostea
  • Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyethylene glycol monolaurate, polyethylene glycol Polyoxyethylene fatty acid esters such as rumonostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene Polyoxyethylene higher alkyl ethers such as polyether ethylene; polyoxyethylene higher alkyl aryl ethers such as polyoxyethylene octylphenyl ether; polyoxyethylene nonylphenyl ether; and the like. it can.
  • nickel carbonate or nickel hydroxide is dissolved in an aqueous ammonia solution containing a carbonate (hydrogen) salt, and the droplets of the aqueous solution of the nickel salt thus obtained are finely dispersed in a nonaqueous solvent.
  • the nickel salts precipitate in the droplets of the aqueous nickel salt solution in the emulsion, and if necessary, the vaporizable components mainly composed of water are further evaporated from the droplets in the emulsion. Then, the nickel salt in the droplets is dried in oil, and the nickel salt thus obtained is centrifuged, washed, and dried to obtain the desired fine particles of Nigel carbonate. Jo particles can be obtained.
  • Cobalt carbonate, cobalt hydroxide, as c another embodiment is also the same for copper carbonate or copper hydroxide, in particular, the nickel carbonate or nickel hydroxide is dissolved carbonate (hydrogen) salts Complex No Anmonia solution, thus Nickel salt obtained by A water / water emulsion is finely dispersed in a non-aqueous solvent to form a W / 0 emulsion, and then, if necessary, agitate or aerate under normal pressure while heating, or aspirate under reduced pressure
  • the nickel salt is precipitated in the droplets of the aqueous nickel salt solution in the emulsion by evaporating the vaporizable components mainly consisting of ammonia, carbon dioxide, and water, and then the spherical precipitate is removed as appropriate.
  • fine spherical particles of nickel carbonate can be obtained.
  • a nickel hydroxide was dissolved in aqueous ammonia containing no carbonate (hydrogen) salt, and the aqueous solution droplets thus obtained were dispersed finely in a non-aqueous solvent. After that, if necessary, while heating, agitation or aeration under normal pressure, or suction under reduced pressure to evaporate the vaporizable components mainly consisting of ammonia, Precipitate nickel hydroxide in the droplets of the aqueous solution, and if necessary, further evaporate the vaporizable components mainly consisting of water from the droplets in the emulsion, and dry the hydroxide in the droplets in oil The nickel hydroxide thus obtained is centrifuged, washed, and dried, for example, to obtain the desired fine nickel hydroxide particles. The same applies to cobalt hydroxide or copper hydroxide.
  • the emulsion containing such droplets is used as it is or is necessary.
  • the above-mentioned nickel hydroxide is collected by appropriate means, for example, centrifugation or filtration, washed and dried to obtain uniform fine particles of the desired Nigel hydroxide. I can do it.
  • cobalt hydroxide or copper hydroxide is the same applies to cobalt hydroxide or copper hydroxide.
  • the temperature and pressure conditions are not particularly limited, but are usually lower than atmospheric pressure, preferably 400 mm. if H g or less reduced pressure (vacuum) lower - well, the other, the upper limit of the reduced pressure (vacuum) is primarily the force due to economics ⁇ , and is usually 5 mm H g. Also, the temperature may range from 0 to 9 O'C, but preferably 1
  • the emulsion is heated to a temperature in the range of 20-70.C, Good results can be obtained by evaporating ammonia and other vaporizable components from the emulsion under reduced pressure using an aspirator, and thus under reduced pressure of about 10 to 50 mmHg.
  • the emulsion in order to evaporate the vaporizable component containing ammonia from the emulsion containing droplets of the aqueous solution of nickel salt, as another method, the emulsion is simply stirred under normal pressure. Is also good. Alternatively, air may be blown into the emulsion under normal pressure and, if necessary, while heating, that is, aeration may be performed.
  • a carbonate or hydroxide of nickel, cobalt or copper is dissolved in an aqueous solution of ammonia (and the second basic compound), and the aqueous solution is converted into fine droplets to form a non-aqueous medium.
  • an acid is added to the emulsion to neutralize the ammonia in the droplets, preferably the droplets, thereby causing nickel, cobalt or copper carbonate or water in the droplets.
  • the oxides are precipitated, precipitated and dried in oil as described above, and the carbonate or hydroxide thus obtained is subjected to, for example, centrifugation, washing and drying.
  • Fine spherical particles of the carbonate or hydroxide described above can be obtained.
  • any of an inorganic acid and an organic acid can be used.
  • the inorganic acid include, for example, nitric acid, hydrochloric acid, and sulfuric acid.
  • Specific examples of the organic acid include, for example, formic acid, oxalic acid, and vinegar. Acids, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-tonolenesulfonic acid and the like can be mentioned. Of these, inorganic acids are preferably used, and nitric acid is particularly preferably used. Industrial applicability
  • a carbonate or hydroxide of nickel, cobalt or copper is dissolved in an aqueous ammonia solution, and the obtained aqueous solution is dispersed in a non-aqueous medium to form droplets of the aqueous solution.
  • nickel, cobalt or copper carbonate or hydroxide is precipitated in the droplet by removing vaporizable components including ammonia from the droplet, thereby forming nickel, Fine spherical particles of cobalt or copper carbonate or hydroxide can be obtained.
  • Such particles of nickel carbonate, cobalt carbonate, copper carbonate, nickel hydroxide, cobalt hydroxide or copper hydroxide obtained by the method of the present invention are, for example, those in which conventional nickel carbonate is amorphous or non-spherical. Since they are fine spherical particles, they themselves are useful as organic synthesis catalysts, carriers, pigments, fillers, glazes, etc., and of course, such carbonates and hydroxides obtained by the present invention.
  • the particles, preferably uniformly fine spherical particles are oxidized as necessary, and then reduced to obtain uniformly fine spherical metallic nickel, cobalt or copper fine powder.
  • metal nickel fine powder can be particularly suitably used, for example, as a material for an internal electrode of a multilayer ceramic capacitor.
  • a nonionic surfactant polyoxyethylene sorbitan monooleate having an HLB value of 15 (Reodol TW—0120 manufactured by Kao Corporation) was added. 30 g was added, and the mixture was stirred at 50 and dissolved.
  • a nonionic surfactant sorbitan monoester (KAO) with an HL value of 4.3 was added to 800 g of super squalane with a boiling point of about 280 ⁇ (Squalane, manufactured by SQUATEC Co., Ltd.) 50 g of Reodol SR-0110) manufactured by Co., Ltd. was added, and the mixture was stirred at 80'C to dissolve.
  • the emulsion is sucked under a reduced pressure of 20 to 3 OmmHg to evaporate a vaporizable component mainly composed of ammonia and carbon dioxide, thereby precipitating basic nickel carbonate in droplets of the emulsion. I let it. Thereafter, the emulsion was further sucked under the reduced pressure to evaporate a vaporizable component containing water as a main component, and the basic nickel carbonate spherical particles generated in the emulsion droplets were dried in oil.
  • the particles of the basic nickel carbonate are centrifuged, washed in the order of hexane, methanol and water, and then dried at a temperature of 100 ° C. for 2 hours to obtain a particle diameter of 0.1 to 6 ⁇
  • a powder of spherical particles of basic nickel carbonate having a diameter of 1.5 tm was obtained. It was confirmed from the X-ray diffraction diagram shown in FIG. 1 that the particles thus obtained were basic nickel carbonate.
  • FIG. 2 shows a scanning electron micrograph of the basic nickel carbonate particles
  • FIG. 3 shows the particle size distribution.
  • Example 2 The powder of the basic nickel carbonate spherical particles obtained in Example 1 was heated at 50 / h, and calcined in an air atmosphere at 600 ° C. for 2 hours to obtain nickel oxide particles. Was. It was confirmed by X-ray diffraction that the product was nickel oxide. Then, the temperature of the nickel oxide particles was raised to 100 ° C. in a hydrogen stream of 3 L / min, and the temperature was raised to 600 ° C. The mixture was reduced with C for 1 hour to obtain spherical nickel powder having a particle size of 0.1 to 5 m and an average particle size of 1.3. The nickel fine powder thus obtained was confirmed from the X-ray diffraction diagram shown in FIG. Fig. 5 shows a scanning electron micrograph of the nickel metal fine powder, and Fig. 6 shows the particle size distribution.
  • Example 2 The powder of the basic nickel carbonate spherical particles obtained in Example 1 was heated at 50 / h, and calcined in an air atmosphere at 600 ° C. for 2
  • Example 3 spherical particles of basic nickel carbonate having a particle size of 1 to 5 m and an average particle size of 1.3 / m were obtained.
  • Example 3 spherical particles of basic nickel carbonate having a particle size of 1 to 5 m and an average particle size of 1.3 / m were obtained.
  • Example 4 spherical particles of basic nickel carbonate having a particle size of 0.1 to 6 m and an average particle size of 1.5 m were obtained.
  • Example 4 spherical particles of basic nickel carbonate having a particle size of 0.1 to 6 m and an average particle size of 1.5 m were obtained.
  • FIG. 7 shows a scanning electron micrograph of the basic nickel carbonate particles.
  • Example 6 Add 14 1 g of commercially available basic nickel carbonate and 33 1 g of potassium bicarbonate to 15% aqueous ammonia, stir well, and remix ammonia with a pH of 9.5. An aqueous solution (1.1 mol / L concentration as Ni) was prepared. Thereafter, in the same manner as in Example 1, powder of spherical particles of basic nickel carbonate having a particle size of 0.1 to 6 m and an average particle size of 1.5 ⁇ m was obtained.
  • Example 7 spherical nickel carbonate powder having a particle size of 0.1 to 10 / m and an average particle size of 1.6 m was obtained.
  • Example 8 a powder of spherical particles of basic nickel carbonate having a particle diameter of 0.1 to 7 ⁇ ⁇ and an average particle diameter of 1.6 im was obtained.
  • Example 8
  • Example 9 Add 14 1 g of commercially available basic nickel carbonate and 33 1 g of lithium hydrogen carbonate to 15% aqueous ammonia, stir well, and mix well with a basic nickel carbonate aqueous solution of lithium hydrogen carbonate mono-ammonia having a pH of 9.5. (1.1 mol ZL concentration as Ni). Thereafter, in the same manner as in Example 1, powder of spherical particles of basic nickel carbonate having a particle size of 0.1 to 10 m and an average particle size of 1.8 m was obtained.
  • Example 9 Example 9
  • Example 10 Add 141 g of commercially available basic nickel carbonate and 331 g of lithium carbonate to 15% aqueous ammonia and stir well to obtain a solution of basic nickel carbonate having a pH of 9.5 in lithium carbonate-ammonia ( 1.1 molno L concentration) was prepared as Ni. Thereafter, in the same manner as in Example 1, powder of spherical particles of basic nickel carbonate having a particle size of 0.1 to 6 m and an average particle size of 1.5 / m was obtained.
  • Example 10 Example 10
  • Example 1 1 1 g of commercially available basic nickel carbonate and 150 g of lithium hydroxide to 15% aqueous ammonia, stir well, and mix well with basic nickel carbonate water with a pH of 9.5. (A concentration of 1.1 mol / L as Ni) was prepared. Thereafter, in the same manner as in Example 1, powder of spherical particles of basic nickel carbonate having a particle size of 0.1 to 6 m and an average particle size of 1.3 / m was obtained.
  • Example 1 2 Add 14 g of commercially available basic nickel carbonate to 15% aqueous ammonia, stir well, and add an aqueous ammonia solution of basic nickel carbonate with a pH of 9.5 (1.1 mol / L as Ni). Concentration) was prepared. Thereafter, in the same manner as in Example 1, powder of spherical particles of basic nickel carbonate having a particle size of 0.1 to 15; m and an average particle size of 4.3 m was obtained; the particles thus obtained. Is basic nickel carbonate. It was confirmed by the X-ray diffraction diagram shown. FIG. 10 shows a scanning electron micrograph of the basic nickel carbonate particles.
  • Example 1 2 shows a scanning electron micrograph of the basic nickel carbonate particles.
  • Example 14 Add 141 g of commercially available basic nickel carbonate and 662 g of a 50% aqueous ethyl acetate solution to 15% aqueous ammonia, stir well, and mix well with ethyl nickel carbonate of pH 9.5. —Aqueous ammonia solution (1.1 mol / L concentration as Ni) was prepared. Thereafter, in the same manner as in Example 1, a powder of spherical particles of basic nickel carbonate having a particle size of 0.1 to 12 m and an average particle size of 2.5 m was obtained.
  • Example 14 Example 14
  • FIG. 11 shows a scanning electron micrograph of the basic nickel carbonate particles.
  • Example 1 Add 14 g of commercially available basic nickel carbonate and 331 g of ethanolamine to a 15% aqueous ammonia solution, and stir well to obtain an aqueous solution of basic nickel carbonate having a pH of 9.5 in ethanolamine-ammonia ( 1.1 mol / L) was prepared as Ni. Then, in the same manner as in Example 1, powder of spherical particles of basic nickel carbonate having a particle size of 0.1 to 20 m and an average particle size of 2.1 m was obtained.
  • Example 1 Example 1
  • Example 18 spherical nickel carbonate powder having a particle size of 0.1 to 13 / m and an average particle size of 3.2 m was obtained.
  • Example 18 spherical nickel carbonate powder having a particle size of 0.1 to 13 / m and an average particle size of 3.2 m was obtained.
  • Example 19 spherical nickel carbonate powder having a particle size of 0.1 to 20 / m and an average particle size of 3.5 m was obtained.
  • Example 19 spherical nickel carbonate powder having a particle size of 0.1 to 20 / m and an average particle size of 3.5 m was obtained.
  • FIG. 14 shows a scanning electron micrograph of the basic nickel carbonate particles.
  • Nigel Hydroxide with pH of 10.8 (0.2 mol / L as Ni) was prepared. Thereafter, in the same manner as in Example 1, nickel hydroxide spherical particles having a particle diameter of 0.1 to 39 / m and an average particle diameter of 6.3 m were obtained.
  • FIG. 15 shows a scanning electron micrograph of the nickel hydroxide particles.
  • the W / 0 type emulsion prepared in the same manner as in Example 1 was stirred at a temperature of 70 ° C. under normal pressure to evaporate a vaporizable component mainly composed of ammonia and carbon dioxide gas.
  • the basic nickel carbonate was precipitated. Thereafter, the mixture was further stirred to evaporate the vaporizable component mainly composed of water, and the particles of basic nickel carbonate formed in the droplets of the emulsion were dried in oil.
  • This basic nickel carbonate is centrifuged, washed with hexane, methanol and water in this order. After that, the powder was dried at 100 ° C. for 2 hours to obtain a powder of spherical basic nickel carbonate particles having a particle size of 0.1 to 25 m and an average particle size of 4.3 m.
  • the W / 0 type emulsion prepared in the same manner as in Example 2 was stirred at a temperature of 70 ° C. under normal pressure to evaporate a vaporizable component mainly composed of ammonia and carbon dioxide gas.
  • the basic nickel carbonate was precipitated. Thereafter, stirring was further continued to evaporate a vaporizable component mainly composed of water, and the basic nickel carbonate particles formed in the emulsion droplets were dried in oil. After centrifuging this basic carbonate nigel, washing it in the order of hexane, methanol and water, it is dried at a temperature of 100 ° C for 2 hours to obtain a particle size of 0.1 to 13 // m.
  • a powder of basic nickel carbonate spherical particles having an average particle diameter of 3.0 / was obtained.
  • FIG. 17 shows a scanning electron micrograph of the basic nickel carbonate particles.
  • the WZO type emulsion prepared in the same manner as in Example 5 was stirred at a temperature of 70 ° C. under normal pressure to evaporate a vaporizable component mainly composed of ammonia and carbon dioxide gas, thereby forming a base in the emulsion droplets.
  • Nickel carbonate was precipitated. Thereafter, the mixture was further stirred to evaporate a vaporizable component mainly composed of water, and the basic nickel carbonate particles formed in the emulsion droplets were dried in oil. This basic nickel carbonate is centrifuged, washed with hexane, methanol and water in this order, dried at a temperature of 100 ° C.
  • a W / 0 type emulsion prepared in the same manner as in Example 20 was stirred at a temperature of 70 ° C. under normal pressure to evaporate a vaporizable component mainly composed of ammonia, and nickel hydroxide was added to the droplets of the emulsion. Was precipitated. Thereafter, stirring was further continued to evaporate a vaporizable component mainly composed of water, and the nickel hydroxide particles generated in the emulsion droplets were dried in oil. The nickel hydroxide is centrifuged, washed in the order of hexane, methanol and water, and dried at a temperature of 100 ° C. for 2 hours to obtain a particle size of 0.1 to 15 m and an average particle size of 2 m.
  • Example 26-W type 0 emulsion prepared in the same manner as in Example 1 was sucked under a reduced pressure of 100 mmHg at a temperature of 5O'C, and vaporized mainly with ammonia and carbon dioxide gas. evaporated ingredients, then t precipitated basic nickel carbonate in the droplets of Emarujon, further continued ⁇ , water evaporated volatile components mainly composed of, in the droplets of the E Marujiyon The resulting basic nickel carbonate particles were dried in oil.
  • the basic nickel carbonate is centrifuged, washed in the order of hexane, methanol and water, dried at a temperature of 100 for 2 hours, and a particle size of 0.1 to 13 // m, average Spherical particles of basic nickel carbonate having a particle size of 2.2 m were obtained.
  • the WZO type emulsion prepared in the same manner as in Example 1 was vacuumed under a reduced pressure of 15 O mm Hg at a temperature of 5 (suctioned with TC to evaporate a vaporizable component mainly composed of ammonia and carbon dioxide gas.
  • the basic nickel carbonate was precipitated in the emulsion droplets by further evaporating the vaporizable component containing water as a main component while continuing stirring.
  • the basic nickel carbonate was centrifuged, washed with hexane, methanol and water in this order, and then dried at a temperature of 100 ° C. for 2 hours to obtain a particle size of 0.1 to 2
  • Example 2 8 Spherical particles of basic nickel carbonate having a particle size of 0 m and an average particle size of 3.0 / m were obtained.
  • Example 2 9 The W / 0 emulsion prepared in the same manner as in Example 1 was sucked at a temperature of 5 O'C under a reduced pressure of 20 OmmHg to evaporate a volatile component mainly composed of ammonia and carbon dioxide gas. Emarujon then c precipitated basic nickel carbonate in the droplets of the further continued stirring, water is evaporated volatile components mainly composed of basic nickel carbonate produced in the droplets of the E Marujon The particles were dried in oil. This basic nickel carbonate is centrifuged, washed with hexane, methanol and water in this order, and dried at a temperature of 100 ° C. for 2 hours to obtain a particle size of 0.1 to 20 / m and an average particle size of 0.1 to 20 / m. Spherical particles of basic nickel carbonate having a diameter of 2.8 m were obtained.
  • the WZO type emulsion prepared in the same manner as in Example 1 was stirred at a normal pressure and at a temperature of 50 ° C. while aerating the air to evaporate a vaporizable component mainly composed of ammonia and carbon dioxide gas.
  • Basic nickel carbonate precipitated in the drops.
  • stirring is further continued to evaporate a vaporizable component mainly composed of water
  • the basic nickel carbonate particles formed in the emulsion droplets were dried in oil.
  • the basic nickel carbonate is centrifuged, washed with hexane, methanol and water in that order, dried at a temperature of 10 ° C. for 2 hours, and a particle size of 0.1 to 18 / m, average Spherical particles of basic nickel carbonate having a particle size of 2.5 m were obtained.
  • Example 30
  • Example 3 1 2 mol 1 L of nitric acid was added dropwise to the W0 type emulsion prepared in the same manner as in Example 1 over about 3 hours to gradually neutralize the emulsion and precipitate basic nickel carbonate.
  • This is filtered, washed in the order of hexane, methanol and water, and then dried at a temperature of 100 ° C. for 2 hours to form a base having a particle size of 0.1 to 15 m and an average particle size of 1.5 m.
  • spherical nickel carbonate particles were obtained.
  • Example 3 2-2 mol 1 ZL of nitric acid was added dropwise to a WZO-type emulsion prepared in the same manner as in Example 5 over about 3 hours, and the droplets were gradually neutralized to obtain a basic nickel carbonate. I started it. This is filtered, washed in the order of hexane, methanol and water, and dried at a temperature of 100 ° C. for 2 hours to obtain a basic carbonate having a particle size of 0.1 to 20 m and an average particle size of 1.8 m. Nickel particles were obtained.
  • Example 3 3 To the W / 0 type emulsion prepared in the same manner as in Example 14 was dropped 2 mo 1 / L nitric acid over about 3 hours, and the droplets were gradually neutralized to precipitate basic nickel carbonate. . This is filtered, washed in the order of hexane, methanol and water, and dried at a temperature of 100 for 2 hours to obtain a basic nickel carbonate having a particle size of 0.1 to 7 m and an average particle size of 2.3 // m. Was obtained.
  • FIG. 19 shows a scanning electron micrograph of the basic nickel carbonate particles.
  • Nitric acid of 2 mol / L was dropped into the W / 0 emulsion prepared in the same manner as in Example 20 over about 3 hours, and the droplets were gradually neutralized to precipitate nickel hydroxide. .
  • This is filtered, washed in the order of hexane, methanol and water, and dried at a temperature of 100 for 2 hours to obtain water having a particle size of 0.1 to 40 / m and an average particle size of 7.5 / m. Spherical particles of nickel oxide were obtained.
  • FIG. 21 shows a scanning electron micrograph of the nickel hydroxide particles.
  • FIG. 25 shows a scanning electron micrograph of the basic copper carbonate particles.
  • N i C0 3. N i (OH) z. 4 H 2 0, below the same 1 4 1 g and bicarbonate Anmoniumu (NH 4 HC 0 3) and 24 2 g 1 5% ammonia water was added, and the mixture was stirred well to prepare an aqueous ammonia monocarbonate ammonium hydrogen carbonate solution (pH: 9.5, concentration: 1.1 mol / L as N L).
  • a 200 g aqueous solution of the nickel salt thus obtained was added to a nonionic surfactant polyoxyethylene sorbitan monooleate having an HLB value of 15 (Reodol TW-0120, manufactured by Kao Corporation). g was added and stirred at 50 ° C. to dissolve.
  • a nonionic surfactant sorbitan monooleate with an HLB value of 4.3 was added to 800 g of super scalane with a boiling point of about 28 O'C (Squalane manufactured by SQUATEC Co., Ltd.) (manufactured by Kao Corporation) 50 g of Reodor (SR_010) was added and stirred at 80 to dissolve.
  • the emulsion was further suctioned under the above-mentioned reduced pressure to evaporate the vaporizable component mainly composed of water, and the spherical nickel carbonate formed in the emulsion droplets was further evaporated. Particles were dried in oil.
  • the particles of the basic nickel carbonate are centrifuged, washed in the order of hexane, methanol and water, and dried at a temperature of 100 ° C. for 2 hours to obtain a particle diameter of 0.2 to 1 m and an average particle diameter of 0.2 to 1 m.
  • a powder of uniformly fine basic nickel carbonate spherical particles having a diameter of 0.5 was obtained.
  • FIG. 27 shows a scanning electron micrograph of the basic nickel carbonate particles thus obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

Procédé de production de fines particules sphériques d'un carbonate ou d'un hydroxyde de nickel, de cobalt ou de cuivre, qui consiste à dissoudre un carbonate ou un hydroxyde de nickel, de cobalt ou de cuivre de formule générale M(CO3)x/2 •(OH)y, dans laquelle M représente Ni, Co ou Cu et x et y sont des nombres répondant à 0 ≤ x ≤ 2, 0 ≤ y ≤ 2 et x + y = 2, dans une solution d'ammoniaque liquide, à convertir la solution qui en résulte en une émulsion de type eau dans l'huile contenant des gouttelettes de la solution dans un milieu non aqueux, puis à éliminer les composants volatils, dont l'ammoniac, de ces gouttelettes de manière à précipiter ainsi un carbonate ou un hydroxyde de nickel, cobalt ou cuivre à l'intérieur de la gouttelette. Ces fines particules sphériques d'un carbonate ou d'un hydroxyde de nickel, cobalt ou cuivre sont non seulement particulièrement utiles en tant que précurseur pour la production de fines particules sphériques homogènes de nickel, cobalt ou cuivre, respectivement, mais sont également utiles, en tant que telles, en tant que catalyseur pour la synthèse organique, véhicule, pigment, charge, glaçure ou analogue.
PCT/JP1999/002634 1998-05-21 1999-05-19 Procede de production de fines particules spheriques de carbonate ou d'hydroxyde de nickel, cobalt ou cuivre WO1999059921A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020007000618A KR100618071B1 (ko) 1998-05-21 1999-05-19 니켈, 코발트 또는 구리의 탄산염 또는 수산화물의 미세구상 입자의 제조 방법
US09/463,021 US6197273B1 (en) 1998-05-21 1999-05-19 Method for producing fine spherical particles of carbonate or hydroxide of nickel, cobalt or copper
EP99921191A EP1013610B1 (fr) 1998-05-21 1999-05-19 Procede de production de fines particules spheriques de carbonate ou d'hydroxyde de nickel, cobalt ou cuivre
DE69911559T DE69911559T2 (de) 1998-05-21 1999-05-19 Verfahren zur herstellung von feinen sferischen teilchen von nikkel, kobalt oder kupfer karbonaten oder hydroxiden

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP13968398 1998-05-21
JP10/139683 1998-05-21
JP10/354188 1998-12-14
JP35418898A JP4174887B2 (ja) 1998-05-21 1998-12-14 ニッケル、コバルト又は銅の炭酸塩又は水酸化物の微細な球状の粒子の製造方法

Publications (1)

Publication Number Publication Date
WO1999059921A1 true WO1999059921A1 (fr) 1999-11-25

Family

ID=26472406

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/002634 WO1999059921A1 (fr) 1998-05-21 1999-05-19 Procede de production de fines particules spheriques de carbonate ou d'hydroxyde de nickel, cobalt ou cuivre

Country Status (7)

Country Link
US (1) US6197273B1 (fr)
EP (1) EP1013610B1 (fr)
JP (1) JP4174887B2 (fr)
KR (1) KR100618071B1 (fr)
CN (1) CN1115301C (fr)
DE (1) DE69911559T2 (fr)
WO (1) WO1999059921A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101973591A (zh) * 2010-09-30 2011-02-16 安徽亚兰德新能源材料有限公司 连续法生产球形碳酸钴的方法

Families Citing this family (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6306787B1 (en) * 1998-06-10 2001-10-23 Sakai Chemical Industry Co., Ltd. Nickel hydroxide particles and production and use thereof
JP4385457B2 (ja) * 1999-11-19 2009-12-16 堺化学工業株式会社 微細球状金属ニッケル微粉末の製造方法
TW200624385A (en) 2004-10-27 2006-07-16 Sumitomo Chemical Co Nickel hydroxide powder and method for making same
JP4929674B2 (ja) * 2004-10-27 2012-05-09 住友化学株式会社 球状ニッケル酸リチウム粒子の製造方法および球状の複合酸化物粒子の製造方法
WO2007000075A1 (fr) * 2005-06-27 2007-01-04 Shenzhen Bak Battery Co., Ltd Procédé de préparation d’hydroxyde nickeleux sphérique qui est dopé et d’oxydes métalliques multiples, et pile secondaire au lithium
JP5557981B2 (ja) * 2007-11-13 2014-07-23 赤穂化成株式会社 微粒子水溶性無機塩の製造方法とその製品
CN101544904B (zh) * 2008-03-28 2012-11-14 中国科学院大连化学物理研究所 一种复合金属氧化物催化剂及制备和应用
CN101830522A (zh) * 2009-03-13 2010-09-15 中国科学院福建物质结构研究所 一种具有铁磁性和优异电化学性能的氧化镍微米球及其合成方法
CN102560656B (zh) * 2010-12-22 2015-10-28 中国科学院大连化学物理研究所 微米级花状复合金属碱式碳酸盐的制备方法
KR101350348B1 (ko) 2012-03-16 2014-01-14 주식회사 비츠로셀 세라믹 분말의 합성방법 및 이로부터 합성되는 세라믹 분말, 소결체 및 세라믹 분말의 합성장치
JP6582283B2 (ja) 2015-01-26 2019-10-02 宮崎県 油中ナノ粒子分散体の製造方法
CN104810160B (zh) * 2015-03-30 2018-05-25 安徽师范大学 一种镍铜碱式碳酸盐纳米线阵列、其制备方法及用途
CN106145179B (zh) * 2015-04-08 2018-02-27 天津大学 一种负载四氧化三钴的氧化铜纳米棒及其合成方法
US10046315B2 (en) 2015-12-15 2018-08-14 Uop Llc Crystalline transition metal molybdotungstate
US10053637B2 (en) 2015-12-15 2018-08-21 Uop Llc Transition metal tungsten oxy-hydroxide
US10322404B2 (en) 2015-12-15 2019-06-18 Uop Llc Crystalline transition metal oxy-hydroxide molybdate
US10233398B2 (en) 2015-12-15 2019-03-19 Uop Llc Crystalline transition metal oxy-hydroxide molybdotungstate
US10052614B2 (en) 2015-12-15 2018-08-21 Uop Llc Mixed metal oxides
US10399065B2 (en) 2015-12-15 2019-09-03 Uop Llc Crystalline transition metal tungstate
US10399063B2 (en) 2015-12-15 2019-09-03 Uop Llc Mixed metal oxides
US10232357B2 (en) 2015-12-15 2019-03-19 Uop Llc Crystalline ammonia transition metal molybdate
US10449523B2 (en) 2015-12-15 2019-10-22 Uop Llc Crystalline bis-ammonia transition metal molybdotungstate
US10005812B2 (en) 2015-12-15 2018-06-26 Uop Llc Transition metal molybdotungsten oxy-hydroxide
US10400181B2 (en) 2015-12-15 2019-09-03 Uop Llc Crystalline bis-ammonia metal molybdate
US10052616B2 (en) 2015-12-15 2018-08-21 Uop Llc Crystalline ammonia transition metal molybdotungstate
CN105609739B (zh) * 2016-02-26 2019-02-26 浙江大学 四氧化三钴/氧化铜复合材料、制备方法和用途
CN106430332A (zh) * 2016-10-08 2017-02-22 南京寒锐钴业股份有限公司 一种减少沉淀过程中母液排放量和沉淀剂单耗的方法
CN110734098B (zh) * 2017-03-08 2022-08-09 尤米科尔公司 用于可再充电锂离子电池的阴极材料的前体
US10773245B2 (en) 2017-08-25 2020-09-15 Uop Llc Crystalline transition metal molybdotungstate
US10882030B2 (en) 2017-08-25 2021-01-05 Uop Llc Crystalline transition metal tungstate
US10843176B2 (en) 2017-12-20 2020-11-24 Uop Llc Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds
US11117811B2 (en) 2017-12-20 2021-09-14 Uop Llc Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds
US11078088B2 (en) 2017-12-20 2021-08-03 Uop Llc Highly active multimetallic materials using short-chain alkyl quaternary ammonium compounds
US10995013B2 (en) 2017-12-20 2021-05-04 Uop Llc Mixed transition metal tungstate
US11007515B2 (en) 2017-12-20 2021-05-18 Uop Llc Highly active trimetallic materials using short-chain alkyl quaternary ammonium compounds
US11034591B2 (en) 2017-12-20 2021-06-15 Uop Llc Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds
US10875013B2 (en) 2017-12-20 2020-12-29 Uop Llc Crystalline oxy-hydroxide transition metal molybdotungstate
US10822247B2 (en) 2017-12-20 2020-11-03 Uop Llc Highly active trimetallic materials using short-chain alkyl quaternary ammonium compounds
US10737248B2 (en) 2018-06-26 2020-08-11 Uop Llc Crystalline transition metal tungstate
US10682632B2 (en) 2018-06-26 2020-06-16 Uop Llc Transition metal tungstate material
US11033883B2 (en) 2018-06-26 2021-06-15 Uop Llc Transition metal molybdotungstate material
US10737249B2 (en) 2018-06-26 2020-08-11 Uop Llc Crystalline transition metal molybdotungstate
US10688479B2 (en) 2018-06-26 2020-06-23 Uop Llc Crystalline transition metal tungstate
US10737246B2 (en) 2018-06-29 2020-08-11 Uop Llc Poorly crystalline transition metal tungstate
US10981151B2 (en) 2018-06-29 2021-04-20 Uop Llc Poorly crystalline transition metal molybdotungstate
US10933407B2 (en) 2018-12-13 2021-03-02 Uop Llc Ammonia-free synthesis for Al or Si based multimetallic materials
US11213803B2 (en) 2018-12-13 2022-01-04 Uop Llc Ammonia-free synthesis for Al or Si based multimetallic materials
US11426711B2 (en) 2019-05-22 2022-08-30 Uop Llc Method of making highly active metal oxide and metal sulfide materials
CN112010357B (zh) * 2019-05-30 2023-11-07 荆门市格林美新材料有限公司 一种小粒径、高密度碳酸钴的制备方法
CN113044888B (zh) * 2019-12-26 2024-06-18 荆门市格林美新材料有限公司 一种无定型碳酸钴的制备方法
CN115888718B (zh) * 2022-10-26 2024-06-18 福州大学 一种板栗状空心NiCu复合材料的制备和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5317787A (en) * 1976-08-03 1978-02-18 Agency Of Ind Science & Technol Filler for high speed liquid chromatography
JPH01301502A (ja) * 1988-02-18 1989-12-05 Mitsubishi Mining & Cement Co Ltd セラミックマイクロ球の製造方法
JPH0259432A (ja) * 1987-10-16 1990-02-28 Agency Of Ind Science & Technol 微小球状多孔性塩基性炭酸ニッケル（２）粒子の製造法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE399719B (sv) * 1976-06-15 1978-02-27 Mx Processer Reinhardt Forfarande for utvinning av metaller ur en blandning av metallhydroxider
JPS5321099A (en) * 1976-08-10 1978-02-27 Agency Of Ind Science & Technol Fine spherical porovs cobalt ( ) carbonate particles and production thereof
CA1273647A (fr) * 1987-08-19 1990-09-04 Jean V. Sang Production de poudres cerames par precipitation de l'emulsion, et poudres ainsi obtenues
BE1002001A4 (fr) * 1988-02-18 1990-05-15 Mitsubishi Mining & Cement Co Procede de preparation de microspheres ceramiques.
DE3834774C2 (de) * 1988-10-12 1995-01-05 Fraunhofer Ges Forschung Verfahren zur Herstellung einer kugelförmige Oxidteilchen enthaltenden Suspension
JP2555475B2 (ja) * 1990-10-16 1996-11-20 工業技術院長 無機質微小球体の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5317787A (en) * 1976-08-03 1978-02-18 Agency Of Ind Science & Technol Filler for high speed liquid chromatography
JPH0259432A (ja) * 1987-10-16 1990-02-28 Agency Of Ind Science & Technol 微小球状多孔性塩基性炭酸ニッケル（２）粒子の製造法
JPH01301502A (ja) * 1988-02-18 1989-12-05 Mitsubishi Mining & Cement Co Ltd セラミックマイクロ球の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1013610A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101973591A (zh) * 2010-09-30 2011-02-16 安徽亚兰德新能源材料有限公司 连续法生产球形碳酸钴的方法

Also Published As

Publication number Publication date
KR100618071B1 (ko) 2006-08-30
DE69911559T2 (de) 2004-08-05
CN1274335A (zh) 2000-11-22
EP1013610B1 (fr) 2003-09-24
JP4174887B2 (ja) 2008-11-05
DE69911559D1 (de) 2003-10-30
EP1013610A4 (fr) 2001-08-16
EP1013610A1 (fr) 2000-06-28
KR20010022049A (ko) 2001-03-15
CN1115301C (zh) 2003-07-23
US6197273B1 (en) 2001-03-06
JP2000044252A (ja) 2000-02-15

Similar Documents

Publication Publication Date Title
WO1999059921A1 (fr) Procede de production de fines particules spheriques de carbonate ou d'hydroxyde de nickel, cobalt ou cuivre
JP4385457B2 (ja) 微細球状金属ニッケル微粉末の製造方法
CN111566047B (zh) 中空二氧化硅颗粒的制造方法
JP2009508795A (ja) 炭酸セリウム粉末及び製法、これから製造された酸化セリウム粉末及び製法、これを含むｃｍｐスラリー
US4999323A (en) Production of ceramic powders by emulsion precipitation processes and the products thereof
CN102884002A (zh) 晶体氧化铈及其制备方法
JP2017023292A (ja) 多孔質シリカ、及びそれを含む消臭剤
CN109174102A (zh) 一种褶皱纳米rGO复合材料的制备方法及褶皱纳米金属氧化物的制备方法
CN113891924B (zh) 具有表面凸块的球状无机颗粒以及其制备方法
CN112584929B (zh) 氨氧化用催化剂的制造方法和丙烯腈的制造方法
KR20180005589A (ko) 니켈 미립자의 개질 방법 및 니켈 미립자의 제조 방법
Baqiya et al. Precipitation process of CaCO3 from natural limestone for functional materials
JP4687217B2 (ja) 排ガス浄化用触媒およびその製造方法
KR100417529B1 (ko) 글리코 써멀법에 의한 나노 크기 세리아 분말의 제조방법
JP2023095008A (ja) 金属酸化物の製造方法
JPH11335709A (ja) 微細球状金属ニッケル微粉末の製造方法
CN113120942A (zh) 一种纺锤形碳酸铈及其氧化铈的合成方法
WO2005108284A1 (fr) Méthode et appareil pour produire une poudre d'oxyde composite
KR101720205B1 (ko) 다공성 금속산화물 분말의 제조 방법
JP2001089803A (ja) 微細球状金属粉末の製造方法
CN115364788B (zh) 基于微流控技术制备稀土氧化物纳米颗粒的方法
JPH0680415A (ja) 金属化合物球形粒子の製造方法
JP6775172B2 (ja) 沈殿触媒の製造方法
JPH11349324A (ja) 希土類酸化物および希土類含有複合酸化物中空粒子の製造
Shi et al. Preparation of ultrafine γ-Al 2 O 3 particles in non-ionic water in oil microemulsions

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 99801187.8

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): CN KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1020007000618

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1999921191

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 09463021

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1999921191

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020007000618

Country of ref document: KR

WWG Wipo information: grant in national office

Ref document number: 1999921191

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1020007000618

Country of ref document: KR